Liquid carbon dioxide absorbents, methods of using the same, and related systems

ABSTRACT

A carbon dioxide absorbent composition is described, including (i) a liquid, nonaqueous silicon-based material, functionalized with one or more groups that either reversibly react with CO 2  or have a high-affinity for CO 2 , and (ii) a hydroxy-containing solvent that is capable of dissolving both the silicon-based material and a reaction product of the silicon-based material and CO 2 . The absorbent may be utilized in methods to reduce carbon dioxide in an exhaust gas, and finds particular utility in power plants.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is Divisional Application of U.S. patent application Ser. No. 13/332,843 (and claims priority therefrom), filed on Dec. 21, 2011, which itself is a continuation-in-part of U.S. patent application Ser. No. 12/512,577, filed on Jul. 30, 2009, which is a continuation-in-part of application Ser. No. 12/343,905, filed on Dec. 24, 2008. The present application is also related to U.S. patent application Ser. No. 12/512,105, filed on Jul. 30, 2009; and now issued as U.S. Pat. No. 8,030,509. The contents of the three Applications and the issued patent are incorporated herein by reference, to the extent they are consistent with the definitions utilized herein.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH & DEVELOPMENT

This invention was made with Government support under grant number DE-NT0005310 awarded by the Department of Energy-NETL. The Government has certain rights in the invention.

BACKGROUND

Pulverized coal (PC) power plants currently produce over half the electricity used in the United States. In 2007, these plants emitted over 1900 million metric tons of carbon dioxide (CO₂), and as such, accounted for 83% of the total CO₂ emissions from electric power generating plants and 33% of the total US CO₂ emissions. Eliminating, or even reducing, these emissions will be essential in any plan to reduce greenhouse gas emissions.

Separating CO₂ from gas streams has been commercialized for decades in food production, natural gas sweetening, and other processes. Aqueous monoethanolamine (MEA) based solvent capture is currently considered to be the best commercially available technology to separate CO₂ from exhaust gases, and is the benchmark against which future developments in this area will be evaluated. Unfortunately, such amine-based systems were not designed for processing the large volumes of flue gas produced by a PC plant. Scaling the MEA-based CO₂ capture system to the size required for PC plants would result in an 83% increase in the overall cost of electricity for the PC plant. Applying this technology to all existing PC plants in the US would cost $125 billion per year, making MEA-based CO₂ capture an unlikely choice for large-scale commercialization.

There are many properties that desirably would be exhibited, or enhanced, in any CO₂ capture technology contemplated to be a feasible alternative to the currently utilized MEA-based systems. For example, any such technology would desirably exhibit a high net CO₂ capacity, and could provide lower capital and operating costs (less material volume required to heat and cool, therefore less energy required). A lower heat of reaction would mean that less energy would be required to release the CO₂ from the material. Desirably, the technology would not require a pre-capture gas compression so that a high net CO₂ capacity could be achieved at low CO₂ partial pressures, lowering the energy required for capture.

Moreover, CO₂ capture technologies utilizing materials with lower viscosities would provide improved mass transfer, reducing the size of equipment needed, as well as a reduction in the cost of energy to run it. Low volatility and high thermal, chemical and hydrolytic stability of the material(s) employed could reduce the amount of material needing to be replenished, and could reduce the emission of degradation products. Of course, any such technology would also desirably have low material costs so that material make-up costs for the system would be minimized. Operability of CO₂ release at high pressures could reduce the energy required for CO₂ compression prior to sequestration. These technologies would also desirably exhibit reduced corrosivity to help reduce capital and maintenance costs, and further would not require significant cooling to achieve the desired net CO₂ loading, reducing operating costs.

In some cases, it would be very desirable if the new CO₂ capture technology could maintain reaction materials and reaction products in a liquid state on a relatively consistent basis. This would also allow better handling and transport of the materials through the CO₂ capture systems, and could also contribute to lower operating costs.

Unfortunately, many of the above delineated desired properties interact and/or depend on one another, so that they cannot be varied independently; and trade-offs are required. For example, in order to have low volatility, the materials used in any such technology typically must have a fairly large molecular weight; but to have low viscosity, the materials must have a low molecular weight. To have a high CO₂ capacity at low pressures, the overall heat of reaction needs to be high; but to have low regeneration energy, the overall heat of reaction needs to be low. Moreover, as of this time, it has been very difficult (if not impossible) to find CO₂ capture materials that have relatively high CO₂ absorbance capabilities, but that can also remain in a liquid state throughout the capture process.

Desirably, a CO₂ capture technology would be provided that optimizes as many of the above desired properties as possible, yet without causing substantial detriment to other desired properties. At a minimum, in order to be commercially viable, such technology would desirably be low cost; and would utilize materials(s) having low volatility and high thermal stability. The materials should also have a high net capacity for CO₂; and the capacity to remain in the liquid state during the CO₂ capture process.

BRIEF DESCRIPTION

In a first aspect, there is provided a carbon dioxide absorbent comprising (i) a liquid, nonaqueous silicon-based material, functionalized with one or more groups that reversibly react with CO₂ and/or have a high-affinity for CO₂; and (ii) a hydroxy-containing solvent that is capable of dissolving both the silicon-based material and a reaction product of the silicon-based material and carbon dioxide

Also, a second aspect provides a method for reducing the amount of carbon dioxide in a process stream comprising contacting the stream with a carbon dioxide absorbent comprising (i) a liquid, nonaqueous, silicon-based material, functionalized with one or more groups that reversibly react with CO₂ and/or have a high-affinity for CO₂, and (ii) a hydroxy-containing solvent, as mentioned above and further described below.

In a third aspect, a power plant is provided, comprising a carbon dioxide removal unit, and further comprising a carbon dioxide absorbent, as described herein.

A method of generating electricity with reduced carbon dioxide emissions is also provided. The method comprises combusting a fuel (pulverized coal, liquid hydrocarbon, natural gas and the like), and directing the flue gas comprising carbon dioxide to an electricity-generating system, e.g. a steam or gas turbine, and then to a carbon dioxide removal unit comprising a carbon dioxide absorbent, as described herein.

DETAILED DESCRIPTION

Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this invention belongs. The terms “first”, “second”, and the like, as used herein, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. Also, the terms “a” and “an” do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced items, and the terms “front”, “back”, “bottom”, and/or “top”, unless otherwise noted, are merely used for convenience of description, and are not limited to any one position or spatial orientation.

If ranges are disclosed, the endpoints of all ranges directed to the same component or property are inclusive and independently combinable (e.g., ranges of “up to about 25 wt. %”, or, more specifically, “about 5 wt. % to about 20 wt. %”, is inclusive of the endpoints and all intermediate values of the ranges of “about 5 wt. % to about 25 wt. %,” etc.). The modifier “about” used in connection with a quantity is inclusive of the stated value, and has the meaning dictated by the context (e.g., it includes the degree of error associated with measurement of the particular quantity).

The subject matter disclosed herein relates generally to carbon dioxide absorbents, power plants incorporating them, and methods of using the absorbents to absorb carbon dioxide from process streams, e.g., as may be produced by methods of generating electricity. Conventional carbon dioxide absorbents lack one or more of the properties considered important, if not critical, in the commercial feasibility of their use in many technologies. MEA-based aqueous absorbents, for example, were not designed for use with large volumes of exhaust gas. As a result, use of these absorbents in such processes is extremely energy-intensive and costly—too costly for implementation into power plants for post combustion CO₂ capture. Moreover, the use of CO₂ absorbents and related reaction products that cannot remain in the liquid state throughout the CO₂ capture process would represent another problem for commercial feasibility, as described herein.

Embodiments of the present invention are directed to carbon dioxide absorbents comprising liquid, nonaqueous silicon-based materials, and a hydroxy-containing solvent. Silicon-based materials are defined as molecules having between one and twenty repeat units, and thus, may include small molecules comprising silicon, i.e., molecules comprising from one to five silicon atoms, or oligomeric materials comprising between about 5 and 20 silicon atoms.

In one embodiment, the present absorbent comprises a CO₂-philic, silicon-containing oligomer, e.g., comprising less than about 20 repeating, monomeric units, and desirably from about 5 to about 10 repeating monomeric units. As used herein, the term “CO₂-philic silicon containing oligomer” means an oligomer that has an affinity for CO₂, as may be evidenced by solubility in liquid or supercritical CO₂, or an ability to physically absorb CO₂

In some particular embodiments, the silicone materials are well-suited for use in the present absorbents. Also correctly referred to as polymerized siloxanes or polysiloxanes, silicones are mixed inorganic-organic polymers or oligomers with the chemical formula [R₂SiO]_(n), wherein R comprises a linear, branched or aromatic organic group of any number of carbons, e.g., methyl ethyl, phenyl, etc. These materials thus comprise an inorganic silicon-oxygen backbone ( . . . Si—O—Si—O—Si—O— . . . ) with organic side groups attached to the silicon atoms, which are four-coordinate. These silicones may be linear, with R and OR′ end-capping groups; or may be cyclic in structure, containing only the repeating units. An example of the latter is octamethylcyclotetrasiloxane. Branched silicones can also be used.

Silicones have low volatility, even at short chain lengths, and in the liquid state at room temperature. They are typically low cost, and stable at high temperatures, e.g., up to about 150° C. Silicones are also readily functionalized, and so, can be functionalized with groups that increase their affinity for CO₂.

The length of the silicone oligomer chain can be easily controlled during synthesis, thereby allowing control of such physical properties as viscosity and boiling point. In addition, siloxane bonds are thermally stable and hydrolytically stable in the absence of strong acids or bases. Many silicone precursors are commercially available, and so advantageously, large scale production capabilities would not have to be developed. Many of these may be utilized in the present invention. One example of a silicone suitable for functionalization in the present invention, and available from a variety of sources, comprises polyhydridomethylsiloxane.

In another embodiment, the present absorbent comprises a CO₂-philic, silicon-based small molecule, e.g., comprising from about one to about five silicon atoms. As used herein, the term “CO₂-philic silicon-based small molecule” means a material that reversibly reacts with or has an affinity for CO₂.

The silicon-based small molecules may comprise one silicon atom as shown in Formula (I), wherein L=a linking group of C₁-C₁₈, and may be aliphatic, aromatic, heteroaliphatic, heteroaromatic or mixtures thereof:

In formula (I), R₁, R₂, R₃ may be the same or different, and may be C₁-C₁₈ aliphatic, aromatic, heteroaliphatic, heteroaromatic or mixtures thereof and R₄=NR₅R₆ where at least one of R₅ or R₆ is H. The other may be C₁-C₁₈ aliphatic, aromatic, heteroaliphatic, heteroaromatic or mixtures thereof.

In some embodiments, the silicon-based materials may be as shown in Formulas II-VI. When x≤5, y+z≤5 and/or r≤5, these materials would generally be considered to be silicon-based small molecules. Alternatively, when x≥5, y+z≥5 and/or r≥5, these silicon based materials would generally be considered to be silicon-containing oligomers. As depicted in structures the core of the silicon-based small molecule may be linear, cyclic, branched, or combinations of these configurations. In most embodiments related to these formulae, “x” and “y+z” each have a value no greater than about 20; while the “r” value is usually no greater than about 10.

For Formula II, R₇-R₁₂ may be the same or different. At least one of R₇-R₁₂ will desirably be L-R₄, while the remainder are desirably C₁-C₁₈ aliphatic, aromatic, heteroaliphatic, heteroaromatic, or mixtures thereof.

For formula III, R₁₃-R₁₆ may be the same or different. At least one of R₁₃-R₁₆ will desirably be L-R₄, while the remainder are desirably C₁-C₁₈ aliphatic, aromatic, heteroaliphatic, heteroaromatic or mixtures thereof. R₁₆ is SiRR′R″, wherein R, R′ and R″ may be the same or different, and may be C₁-C₁₈ aliphatic, aromatic, heteroaliphatic, heteroaromatic or mixtures thereof, and may be L-R₄.

For formulae IV, V, and VI, R₁₈-R₂₃ and R₂₄-R₂₅ and R₂₆-R₃₅ may be the same or different; and at least one of R₁₈-R₂₃=L-R₄; at least one of R₂₄-R₂₅=L-R₄; and at least one of R₂₆-R₃₅=L-R₄, and the rest may be C₁-C₁₈ aliphatic, aromatic, heteroaliphatic, heteroaromatic, or mixtures thereof. A related proviso is that R₂₃ is SiRR′R″, wherein R, R′ and R″ may be the same or different, and may be C₁-C₁₈ aliphatic, aromatic, heteroaliphatic, heteroaromatic or mixtures thereof, and may be L-R₄.

The silicon-based material may desirably be functionalized with groups that enhance its net capacity for CO₂. Functional groups that are expected to be CO₂-philic, and react with CO₂ in a silicon-based material they functionalize, include any of those including a nitrogen atom, such as, for example aliphatic amines, imines, amidines, amides, heterocyclic amino compounds such as pyridine, aromatic amines such as aniline, and the like, as well as combinations of any of these. The particular functional group utilized will depend upon the silicon-based material chosen. For those embodiments wherein the silicon-based material comprises a siloxane, amine functionality may be suitable, since many aminosiloxanes are readily commercially available, and are readily further functionalized if desired or required, in order to increase CO₂ reactivity. Non-limiting examples of amine functional groups that exhibit CO₂-reactivity include aminomethyl, aminoethyl, aminopropyl, aminoethyl-aminopropyl, aminoethyl-aminoisobutyl, aminoethylaminomethyl, 2-aminopyridyl, piperazine-propyl and imidazoyl propyl.

Functional groups may be located in a side chain, and can also be the end-capping groups. Aminoethyl-aminopropyl siloxane oligomers with functional groups in the side chain are exemplified by the molecule shown below at FIGURE VII. This material has a maximum theoretical CO₂ capacity of about 20 wt %, compared to 10 wt % for 30 wt % aqueous MEA.

One other example of an aminosiloxane with end-capped functional groups suitable for use in the present absorbent is aminopropyl terminated polydimethyldisiloxane, shown below in FIGURE VIII:

One such aminosiloxane is used for hair conditioning, and is commercially available from Gelest, with a number average molecular weight of from about 850 to about 900, and a calculated CO₂ absorption capacity of from about 4.4 to about 5.2%. It is expected that the addition of further amine functionality will result in an increase in this absorption capacity.

Those of ordinary skill in the art of polymer chemistry are well versed in methods of adding functional groups to the backbone of an oligomer useful in the present absorbent. Numerous methods of attachment of functional groups are known such as hydrosilylation and displacement as shown in Michael A. Brook's book Silicon in Organic, Organometallic, and Polymer Chemistry (Wiley VCH Press, 2000).

As alluded to previously, in many cases, silicon-based functionalized materials form solids or very high viscosity oils on reaction with CO₂. This can negatively impact mass transfer, so that the absorbent material does not react with as much CO₂ as is theoretically possible. Furthermore, materials that form solid CO₂ reaction products would not readily fit into existing CO₂ capture process schemes. Therefore, a selected co-solvent is added according to embodiments of this invention. The co-solvent is hydroxy-containing, as explained below, and maintains liquidity on reaction with CO₂, thereby maximizing capture efficiency, and enhancing the compatibility of the selected materials with standard CO₂ capture systems.

The concept of using co-solvents in conjunction with aminoalkanols to absorb CO₂ from mixed gas streams was generally known in the art. Reference is made, for example, to U.S. Pat. No. 4,112,051, issued to Sartori et al. However, the success of this approach with materials that are much less polar (like many of the silicon-based materials of the present invention) might appear doubtful to those skilled in the art. In order to fulfill its function of maintaining solution liquidity, the co-solvent must be very miscible with both the silicon-based material and its CO₂ reaction product. In view of the difference in polarity between typical siloxane materials and hydroxy-containing solvents, identification of suitable solvents was a very difficult task.

Surprisingly, the present inventors identified certain hydroxy-containing solvents that are able to solubilize both the silicon-based materials described above, and their CO₂ reaction products. As used herein, the phrase “hydroxy-containing solvent” means a solvent that has one or more hydroxy groups. The hydroxy-containing solvent also desirably has a low vapor pressure, e.g., below about 150 mm Hg at 100° C.; and often, from about 0.001 to about 30 mm Hg at 100° C., so that minimal loss of the hydroxy-containing solvent occurs via evaporation.

Suitable hydroxy-containing solvents for embodiments of this invention are liquid at room temperature, and are capable of dissolving the silicon-based material and its CO₂ reaction product. In preferred embodiments, the solvents are capable of dissolving the constituents at relatively high concentrations, e.g., at least about 20% of the silicon-based material, and in some preferred embodiments, at least about 40% of the silicon-based materials. In this manner, a stable solution of the silicon-based material and a carbamic-acid salt (one of the typical reaction products) are present as a stable solution.

In preferred embodiments, the hydroxy-containing solvents do not, themselves, substantially chemically react with CO₂. Rather, they serve as a medium for CO₂ transfer to the functionalized silicon-based material. As a result, the hydroxy-containing solvents are expected to be capable of increasing the reaction rate, e.g., by increasing the mass transfer rate, of CO₂ and the silicon-based material, and also to reduce, or substantially prevent, excessive viscosity build-up when the silicon-based material reacts with CO₂. Advantageously, many suitable hydroxyl-containing solvents may be recycled, along with the silicon-based material, if desired.

Examples of suitable hydroxy-containing solvents include, but are not limited to, those comprising one or more hydroxyl groups, such as, glycols, phenols, and hydroxylated silicones. Suitable glycols may include, for example, trimethylolpropane ethoxylates, glycerol, ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol, to name a few. Suitable hydroxylated silicones include, for example, 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane, or the hydrosilylation reaction product of 1,1,3,3-tetramethyldisiloxane and trimethylolpropane allylether. Hydroxy compounds may also be in the form of phenols such as eugenol, isoeugenol, 2-allyl-6-methylphenol, 2-allylphenol and the like.

In certain embodiments, the absorbent may comprise an amount of water, e.g., so that all water need not be removed from the process stream in order to utilize the absorbent and methods. Indeed, in some embodiments, water is desirably present and in such embodiments, can assist in the solubilization of reaction products.

Optionally, the absorbent may also include other components, such as, e.g., oxidation inhibitors to increase the oxidative stability and anti-foaming agents. The use of oxidation inhibitors, also called antioxidants, can be especially advantageous in those embodiments of the invention wherein the functional groups comprise amine groups.

The carbon dioxide absorbents provided herein are expected to provide substantial improvement when utilized to remove CO₂ from process gases, as compared to those currently commercially available and/or utilized for this purpose. As such, a method of reducing the carbon dioxide in a process stream is provided, and comprises contacting the process stream with the carbon dioxide absorbents described herein. The process stream so treated may be any wherein the level of CO₂ therein is desirably reduced, and in many processes, CO₂ is desirably reduced at least in the exhaust streams produced thereby. The process stream is typically gaseous, but may contain solid or liquid particulates, and may be at a wide range of temperatures and pressures, depending on the application.

The carbon dioxide absorbents for embodiments of this invention have low volatility, high thermal stability, and are either commercially available with, or can be provided with, a high net capacity for CO₂, and as such, are appropriate for large scale implementation. And so, there is also provided a power plant utilizing the present absorbents, and a method of utilizing the absorbents in generating electricity with reduced carbon dioxide emissions.

Examples 1-12

Reaction of silicon-based materials with CO₂ in the presence of a hydroxy-containing co-solvent.

To illustrate the ability of the hydroxy-containing co-solvent triethylene glycol to enhance the CO₂ absorption of various silicon-based materials, as well as providing a liquid medium, the following Examples 1-12 were conducted. The silicon-based materials were exposed to 1 atmosphere of CO₂ in the presence of, or not in the presence of, the hydroxyl-containing co-solvent triethylene glycol (at 50 wt %, with the exception of example 4 at 75 wt %) at 40° C. for 2 hours (h) with mechanical stirring.

Comparative Example 1

Into a pre-tared, 25 mL, three-neck, round-bottom flask equipped with a mechanical stirrer, gas inlet and a gas outlet and heated with a temperature controlled oil bath, was charged 2.0707 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane. Dry CO₂ gas was introduced at a rate of ˜50 mL/min into the flask via a glass tube positioned ˜10 mm above the stirring liquid surface. CO₂ exposure continued for 2-h at 40° C. after which time the exterior of the flask was cleaned and the flask weighed. The total weight gain of 0.3588 g corresponded to 71% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was also a solid.

Example 2

2.0194 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane and 2.0174 g of triethylene glycol were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 1. The total weight gain was 0.4089 g. This corresponded to 114% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. In contrast to Example 1, the reaction product here was a liquid.

Comparative Example 3

2.0653 g of aminoethylaminopropyl methylsiloxane oligomer were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 1. The total weight gain was 0.2110 g. This corresponded to 37% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a solid.

Example 4

2.0168 g of aminoethylaminopropyl methylsiloxane oligomer and 4.0292 g of triethylene glycol were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 1. The total weight gain was 0.4803 g. This corresponded to 87% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a liquid, in contrast to comparative Example 3, which did not include triethyleneglycol.

Comparative Example 5

2.0295 g of 1,3-Bis(3-aminoethylaminopropyl)-tetramethyldisiloxane were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 1. The total weight gain was 0.3389 g. This corresponded to 64% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a solid.

Example 6

2.0240 g of 1,3-Bis(3-aminoethylaminopropyl)-tetramethyldisiloxane and 2.0237 g of triethylene glycol were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 1. The total weight gain was 0.4777 g. This corresponded to 90% of the theoretical amount of weight that should have been gained if all of the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a liquid, in contrast to the solid obtained in example 5.

Comparative Example 7

1.1090 g of 1,3,5,7-tetrakis(3-aminopropyl)-tetramethylcyclotetrasiloxane were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 1. The total weight gain was 0.0621. This corresponded to 30% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a solid.

Example 8

1.0722 g of 1,3,5,7-tetrakis(3-aminopropyl)-tetramethylcyclotetrasiloxane and 1.1028 g of triethylene glycol were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 1 The total weight gain was 0.3099 g. This corresponded to 154% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a liquid, in contrast to the solid product obtained in example 7.

Comparative Example 9

1.0498 g of Tetrakis(3-aminopropyl-dimethylsiloxy)silane were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 1. The total weight gain was 0.1445 g. This corresponded to 87% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a solid.

Example 10

1.0662 g of Tetrakis(3-aminopropyldimethylsiloxy)silane and 0.1.1175 g of triethylene glycol were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 1. The total weight gain was 0.1956 g. This corresponded to 116% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a liquid, in contrast to the solid obtained in example 9.

Comparative Example 11

1.2135 g of 1,3-Bis(3,9-dimethyl-5,8,11-trioxa-2-azatetradecan-13-amine) were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 1. The total weight gain was 0.0742 g. This corresponded to 44% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a solid.

Example 12

1.0323 g of 1,3-Bis(3,9-dimethyl-5,8,11-trioxa-2-azatetradecan-13-amine) and 1.0368 g of triethylene glycol were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 1. The total weight gain was 0.0587 g. This corresponded to 41% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a liquid, in contrast to the solid obtained in example 11.

The results of Examples 1-12 are summarized in Table 1, below.

TABLE 1 Co- % of Physical solvent Theoretical state of Example Amine present wt gain product 1 1,3-Bis(3-aminopropyl)tetramethyldisiloxane No 71 S comparative 2 1,3-Bis(3-aminopropyl)tetramethyldisiloxane Yes 114 L 3 Aminoethylaminopropyl methylsiloxane No 37 S comparative oligomer 4 Aminoethylaminopropyl methylsiloxane Yes 87 L oligomer 5 1,3-Bis(3- No 64 S comparative aminoethylaminopropyl)tetramethyldisiloxane 6 1,3-Bis(3- Yes 90 L aminoethylaminopropyl)tetramethyldisiloxane 7 1,3,5,7-tetrakis(3- No 30 S comparative aminopropyl)tetramethylcyclotetrasiloxane 8 1,3,5,7-tetrakis(3- Yes 154 L aminopropyl)tetramethylcyclotetrasiloxane 9 Tetrakis(3-aminopropyldimethylsiloxy)silane No 87 S comparative 10 Tetrakis(3-aminopropyldimethylsiloxy)silane Yes 116 L 11 1,3-Bis(3,9-dimethyl-5,8,11-trioxa-2- No 44 S comparative azatetradecan-13-amine) 12 1,3-Bis(3,9-dimethyl-5,8,11-trioxa-2- Yes 41 L azatetradecan-13-amine)

Examples 13-20

Reaction of a silicon-based material with CO₂ in the presence of various hydroxy-containing co-solvents.

To illustrate the ability of the hydroxy-containing co-solvents triethyleneglycol dimethyl ether and triethyleneglycol to enhance the CO₂ absorption of the silicon-based material, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, as well as to provide a liquid medium, the following Examples 13-20 were conducted. In each, the silicon-based material 1,3-bis(3-aminopropyl)tetramethyldisiloxane was exposed to 1 atmosphere of CO₂ in the presence of or not in the presence of a hydroxyl-containing co-solvent at 40° C. for 2 hours (h), with mechanical stirring.

Comparative Example 13

Into a pre-tared, 25 mL, three-neck, round-bottom flask equipped with a mechanical stirrer, gas inlet and a gas outlet and heated with a temperature controlled oil bath, was charged 2.0707 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane. Dry CO₂ gas was introduced at a rate of ˜50 mL/min into the flask via a glass tube positioned ˜10 mm above the stirring liquid surface. CO₂ exposure continued for 2 h at 40° C. after which time the exterior of the flask was cleaned and the flask weighed. The total weight gain of 0.3588 g corresponded to 71% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was also a solid.

Example 14

2.0261 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane and 2.1198 g of triethyleneglycol dimethyl ether were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 13. The total weight gain was 0.2984 g. This corresponded to 83% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a solid, which contrasts with the liquid product obtained in example 2, using triethylene glycol.

Example 15

2.0366 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane and 4.0306 g of triethyleneglycol dimethyl ether were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 13. The total weight gain was 0.3566 g. This corresponded to 99% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a solid, which contrasts with the liquid product obtained in example 2, using triethylene glycol.

Example 16

2.0194 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane and 2.0174 g of triethyleneglycol were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 13. The total weight gain was 0.4089 g. This corresponded to 114% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a liquid.

Example 17

2.0230 g of triethyleneglycol was charged into a flask and allowed to react with CO₂ according to the procedure described in Example 13. The total weight gain was 0.0004 g. This corresponded to <1% total weight gain. The reaction product in this instance was a liquid, but exhibited relatively poor CO₂ absorbing-capacity for triethylene glycol. This example demonstrates the necessity for having the silicon-based compound present.

Example 18

2.0387 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane and 1.0454 g of triethyleneglycol were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 13. The total weight gain was 0.4071 g. This corresponded to 113% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a solid, in contrast to the reaction product of Example 2. This example demonstrates that, in some instances, there is an optimum ratio of silicone to solvent.

Example 19

2.0178 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane and 4.0734 g of triethyleneglycol were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 13. The total weight gain was 0.4203 g. This corresponded to 118% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a liquid.

Example 20

2.0186 g of 1,3-Bis(3-aminopropyl)-tetramethyldisiloxane, 1.0419 g of triethyleneglycol and 0.2245 g water were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 13. The total weight gain was 0.3545 g. This corresponded to 99% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a liquid in contrast to Example 18. The example demonstrates that, in some instances, the use of additional water can facilitate the formation of a liquid product.

The results of Examples 13-20 are summarized in Table 2, below.

TABLE 2 Wt ratios CO₂ uptake (Amine: (% Physical Example Co-solvent solvent:water) theoretical) state 13 (control) None 100:0:0 71 S 14 Triethyleneglycol 50:50:0 83 S dimethyl ether 15 Triethyleneglycol 33:67:0 99 S dimethyl ether 16 Triethyleneglycol 50:50:0 114 L 17 Triethyleneglycol 0:100:0 — L 18 Triethyleneglycol 67:33:0 113 ~S 19 Triethyleneglycol 33:67:0 118 L 20 Triethyleneglycol 62:31:07 99 L

Table 2 demonstrates that, without a co-solvent, 1,3-bis(3-aminopropyl)tetramethyldisiloxane readily forms a solid material (Example 13). When triethyleneglycol dimethyl ether is added as a co-solvent (Examples 14, 15), solid reaction products are still formed. When triethyleneglycol is added at a 1:1 weight ratio (Example 16) a homogeneous reaction product is formed that, very desirably, remains liquid throughout the capture process. Varying the ratio of co-solvent to capture solvent results in varying degrees of liquidity and viscosity. (Examples 17-20)

Table 2 further demonstrates that the co-solvent alone does not physically absorb a significant amount of CO₂ (Example 17). However, the “mixed system” allows for enhanced capture of CO₂ via a synergistic action of the chemical capture process and physisorption. Water may optionally be present to aid in solubilizing the reaction products (Example 20).

Examples 21-33

Reaction of a silicon-based material with CO₂ in the presence of various hydroxy-containing co-solvents.

To illustrate the ability of various other hydroxy-containing co-solvents (at 50 weight % concentration) to enhance the CO₂ absorption of the silicon-based material, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, as well as to provide a liquid medium, the following Examples 21-33 were conducted. In each example, the silicon-based material 1,3-bis(3-aminopropyl)tetramethyldisiloxane was exposed to 1 atmosphere of CO₂ in the presence of, or not in the presence of, a hydroxyl-containing co-solvent at 40° C. for 2 hours (h) with mechanical stirring.

Comparative Example 21

Into a pre-tared, 25 mL, three-neck, round-bottom flask equipped with a mechanical stirrer, gas inlet and a gas outlet, and heated with a temperature controlled oil bath, were charged 2.0349 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane and 2.0472 g of SF1488 (a silicone polyether available from Momentive Performance Materials). Dry CO₂ gas was introduced at a rate of ˜50 mL/min into the flask, via a glass tube positioned ˜10 mm above the stirring liquid surface. CO₂ exposure continued for 2 h at 40° C., after which time the exterior of the flask was cleaned, and the flask weighed. The total weight gain of 0.2739 g corresponded to 76% of the theoretical amount of weight that should have been gained if all of the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a waxy yellow solid.

Example 22

2.0311 g of 1,3-Bis(3-aminopropyl) tetramethyl-disiloxane and 2.0506 g of a diol terminated disiloxane prepared via the hydrosilylation of trimethylolpropane mono allyl ether with tetramethyl disiloxane were charged into a flask and allowed to react with CO₂, according to the procedure described in Example 21. The total weight gain was 0.3491 g. This corresponded to 97% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a viscous liquid.

Example 23

2.0337 g of 1,3-Bis(3-aminopropyl) tetramethyl-disiloxane and 2.0653 g of tetrathylene glycol were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 21. The total weight gain was 0.4182 g. This corresponded to 116% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a moderately viscous liquid.

Example 24

2.0745 g of 1,3-Bis(3-aminopropyl) tetramethyl-disiloxane and 2.0507 g of poly(propylene glycol) with a molecular weight of 725 were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 21. The total weight gain was 0.3400 g. This corresponded to 92.5% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a solid that formed very quickly on introduction of the gas.

Example 25

1.9957 g of 1,3-Bis(3-aminopropyl) tetramethyl-disiloxane and 2.0630 g of a 3:1 blend of tetraethylene glycol and the diol terminated disiloxane from example B above, were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 21. The total weight gain was 0.3937 g. This corresponded to 111% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a moderately viscous liquid.

Example 26

2.0385 g of 1,3-Bis(3-aminopropyl) tetramethyl-disiloxane and 1.9718 g of trimethyolpropane mono allyl ether were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 21. The total weight gain was 0.3876 g. This corresponded to 107% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a moderately viscous liquid.

Example 27

2.0683 g of 1,3-Bis(3-aminopropyl) tetramethyl-disiloxane and 2.0709 g of eugenol were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 21. The total weight gain was 0.3449 g. This corresponded to 94% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a viscous yellow liquid.

Example 28

2.0291 g of 1,3-Bis(3-aminopropyl) tetramethyl-disiloxane and 1.9965 g of trimethylolpropane ethoxylate (4/15 EO/OH, Mn ˜170) were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 21. The total weight gain was 0.3640 g. This corresponded to 101% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a very viscous yellow liquid.

Example 29

2.0157 g of 1,3-Bis(3-aminopropyl) tetramethyl-disiloxane and 2.0675 g of pentaerythritol ethoxylate (3/4 EO/OH, Mn ˜270) were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 21. The total weight gain was 0.3855 g. This corresponded to 108% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a very viscous liquid.

Example 30

1.9999 g of 1,3-Bis(3-aminopropyl) tetramethyl-disiloxane and 2.0129 g of a 2:1 blend of tetraethylene glycol and eugenol were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 21. The total weight gain was 0.3773 g. This corresponded to 107% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a viscous yellow liquid.

Example 31

2.0391 g of 1,3-Bis(3-aminopropyl) tetramethyl-disiloxane and 2.0640 g of isoeugenol were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 21. The total weight gain was 0.3464 g. This corresponded to 96% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a viscous yellow liquid.

Example 32

2.0379 g of 1,3-Bis(3-aminopropyl) tetramethyl-disiloxane and 2.0447 g of sulfolane were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 21. The total weight gain was 0.3227 g. This corresponded to 89% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a solid that formed very quickly on introduction of the gas.

Example 33

2.0118 g of 1,3-Bis(3-aminopropyl) tetramethyl-disiloxane and 2.0010 g of 2-allyl-6-methylphenol were charged into a flask and allowed to react with CO₂ according to the procedure described in Example 21. The total weight gain was 0.2711 g. This corresponded to 76% of the theoretical amount of weight that should have been gained if all the amine groups had reacted with a stoichiometric amount of CO₂. The reaction product was a light yellow liquid.

Example 33A

1.0258 g of 1,3-Bis(3-aminopropyl)-tetramethyldisiloxane and 1.0266 g glycerol were charged to a flask and allowed to react with CO₂, according to the procedure described above for Example 1. The total weight gain was 0.1888 g. This corresponds to 104% of the theoretical amount of weight that should have been gained if all the amine groups reacted with a stoichiometric amount of CO₂. The final mixture was a liquid.

The results of Examples 21-33 and 33A are summarized in Table 3, below.

TABLE 3 % of Physical Theoretical state of Example Co-Solvent (50 wt %) wt gain product 21 SF1488 Momentive Silicone polyether 76 S Comparative 22 a hydrosilylation reaction product of 1,1,3,3- 97 L tetramethyldisiloxane and trimethylolpropane allyl ether 23 Tetraethylene glycol 116 L 24 Poly(propylene glycol) MW = 725 93 S 25 Mixture of tetraethylene glycol/1,3-bis(3- 111 L hydroxypropyl)tetramethyldisiloxane 3:1 26 Trimethylolpropane allyl ether 107 L 27 Eugenol 94 L 28 Trimethylolpropane ethoxylate Mn = 170 101 L 29 Pentaerythritol ethoxylate Mn = 270 108 L 30 2:1 Tetraethylene glycol/eugenol 107 L 31 Isoeugenol 96 L 32 Sulfolane 89 S comparative 33 2-allyl-6-methylphenol 76 L 33A Glycerol 104 L

Examples 34-50

High Throughput Screening Experiments

The high throughput screening experiments were carried out using a 27 well parallel reactor (React Vap III) from Pierce and a Symyx Core Module for automated weighing in 8 mL glass vials. The experiments were run using technical grade CO₂ at 1 atm and the flow was set at 1.2 mL/h (10000 cm²/min) by using a MKS gas flow controller. Each formulation was tested in triplicate. The co-solvents were purchased from Aldrich or Fisher Scientific and used without further purification.

Each vial was loaded with a stirrer bar and pre-weighed using the Symyx Core module. The vials were then loaded with the corresponding compound (200-300 μL) and the appropriate co solvent (200-300 μL). The resulting mixture was stirred for 15-20 min and treated with CO₂ gas (1 atm) for 60-120 min at the desired temperature (40 and 55° C.). After the CO₂ treatment, the reactor block was cooled down to room temperature and all the vials were transferred to a Symyx Core Module® for automated weighing. The physical state of each vial was visually inspected and recorded. The CO₂ adsorption performance was reported as an average of the % weight gain after each CO₂ treatment. The results of these experiments are shown in Table 4.

TABLE 4 % wt Physical Ex. Silicon-based Material Co-Solvent Wt ratios* %** gain state*** 34 1,3-Bis(3-aminopropyl) triethylene 10:90 175 3.1 L tetramethyldisiloxane glycol 35 1,3-Bis(3-aminopropyl) triethylene 30:70 155 8.2 L tetramethyldisiloxane glycol 36 1,3-Bis(3-aminopropyl) triethylene 50:50 133 11.8 L tetramethyldisiloxane glycol 37 1,3-Bis(3-aminopropyl) N methyl 50:50 118 10.4 L tetramethyldisiloxane pyrrolidone (NMP) 38 1,3-Bis(3-aminopropyl) Tetraglyme 50:50 123 10.9 S Comp tetramethyldisiloxane dimethyl ether 39 Aminoethylaminopropyl triethylene 10:90 165 4.6 L methylsiloxane oligomers glycol 40 Aminoethylaminopropyl triethylene 30:70 122 10.2 L methylsiloxane oligomers glycol 41 Aminoethylaminopropyl triethylene 50:50 44 6.2 L methylsiloxane oligomers glycol 42 Aminoethylaminopropyl N methyl 50:50 56 7.8 S Comp methylsiloxane oligomers pyrrolidone 43 Aminoethylaminopropyl Tetraglyme 50:50 41 5.7 S Comp methylsiloxane oligomers dimethyl ether 44 1,3,5,7-tetrakis(3- N methyl 50:50 84 7.9 S Comp aminopropyl) pyrrolidone tetramethylcyclotetrasiloxane 45 1,3,5,7-tetrakis(3- Tetraglyme 50:50 53 5.0 S Comp aminopropyl) dimethyl tetramethylcyclotetrasiloxane ether 46 1,3- triethylene 10:90 158 5.0 L Bis(aminoethylaminomethyl) glycol tetramethyldisiloxane 47 1,3- triethylene 30:70 117 11.1 L Bis(aminoethylaminomethyl) glycol tetramethyldisiloxane 48 1,3- triethylene 50:50 74 11.7 L Bis(aminoethylaminomethyl) glycol tetramethyldisiloxane 49 1,3- N methyl 50:50 59 9.3 S Comp Bis(aminoethylaminomethyl) pyrrolidone tetramethyldisiloxane 50 1,3- Tetraglyme 50:50 64 10.1 S Comp Bis(aminoethylaminomethyl) dimethyl tetramethyldisiloxane ether *Amine:solvent **of theoretical ***After absorption

Generally speaking, Table 4 shows that capped-hydroxy compounds yielded solid reaction products, while uncapped co-solvents yielded soluble solutions. The amide-based compound, N-methyl pyrrolidone (NMP), did not perform successfully as a solvent.

While only certain features of the invention have been illustrated and described herein, many modifications and changes will occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention. 

The invention claimed is:
 1. A method for reducing the amount of carbon dioxide in a process stream comprising contacting the stream with a carbon dioxide absorbent comprising (i) a liquid, nonaqueous silicon-based material, functionalized with one or more nitrogen atom-containing groups that reversibly react with CO₂ and/or have a high-affinity for CO₂; and (ii) a hydroxy-containing solvent that is capable of dissolving both the silicon-based material and a reaction product of the silicon-based material and carbon dioxide.
 2. The method of claim 1, wherein the process stream comprises an exhaust stream.
 3. The method of claim 1, wherein the hydroxy-containing solvent comprises trimethylolpropane ethoxylates, glycerol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane, a hydrosilylation reaction product of 1,1,3,3-tetramethyldisiloxane and trimethylolpropane allylether, or combinations of these.
 4. The method of claim 1, wherein the carbon dioxide solvent further comprises water.
 5. The method of claim 1, wherein the functionalized silicon-based material comprises one or more aminosilicones.
 6. The method of claim 1, wherein the functionalized silicon-based material comprises silanes, or compounds containing one or more siloxy units, or combinations of thereof.
 7. The method of claim 1, wherein the functional group(s) comprise(s) one or more aliphatic amines, imines, amidines, amides, heterocyclic amino compounds, aromatic amines, and combinations thereof.
 8. The method of claim 1, wherein the functional group(s) comprise(s) one or more amino hydroxy groups.
 9. The method of claim 1, wherein the solvent has a vapor pressure below about 150 mm Hg at 100° C.
 10. The method of claim 1, wherein the absorbent further comprises antioxidants, stabilizers, accelerators, antifoaming agents or blends thereof.
 11. The method of claim 1, wherein the nitrogen atom-containing functional group is not a sterically hindered amine.
 12. The method of claim 1, wherein the functionalized, silicon-based material comprises less than 20 repeating, monomeric units.
 13. The method of claim 12, wherein the functionalized, silicon-based material comprises 10 or less repeating, monomeric units.
 14. The method of claim 1, wherein the solvent comprises two or more hydroxyl groups.
 15. The method of claim 14, wherein the solvent comprises a glycol, a hydroxylated silicone, a phenol, or combinations of the foregoing.
 16. The method of claim 15, wherein the solvent comprises trimethylolpropane ethoxylates, glycerol, triethylene glycol, tetraethylene glycol, 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane, a hydrosilylation reaction product of 1,1,3,3-tetramethyldisiloxane and trimethylolpropane allyl ether, eugenol, isoeugenol, 2-allyl-6-methylphenol, 2-allylphenol or combinations of the foregoing.
 17. The method of claim 1, wherein the functional group(s) comprise(s) one or more amines.
 18. The method of claim 17, wherein the functional group(s) comprise(s) one or more di-, tri- and polyamines, or combinations of the forgoing.
 19. The method of claim 18, wherein the functional group(s) comprise(s) one or more aminoethylaminopropyl piperazinopropyl, aminomethylaminoethyl, 2-aminopropylpyridyl, groups or combinations of these. 